A low boron amorphous alloy having excellent soft magnetic characteristics, composed of B: about 6-10 at %, Si: about 10-17 at %, P: about 0.02-2 at % and the balance Fe and incidental impurities. The invention lowers production costs because the content of expensive boron is reduced.

Patent
   5626690
Priority
Jan 13 1995
Filed
Aug 28 1995
Issued
May 06 1997
Expiry
Aug 28 2015
Assg.orig
Entity
Large
4
4
EXPIRED
1. A low boron amorphous alloy having excellent soft magnetic characteristics, consisting of:
about 6-10 at % B;
about 10-17 at % Si;
about 0.02-2 at % P; and
the balance Fe and incidental impurities.
2. A low boron amorphous alloy having excellent soft magnetic characteristics, consisting of:
about 6-10 at % B;
about 10-17 at % Si;
about 0.02-2 at % P;
about 0.1-2 at % C; and
the balance Fe and incidental impurities.
3. A low boron amorphous alloy cast sheet having excellent soft magnetic characteristics and having an alloy composition according to claim 1, wherein said cast sheet has a mean centerline surface roughness Ra on the casting mold side of about 0.8 μm or less.
4. A low boron amorphous alloy cast sheet having excellent soft magnetic characteristics and having an alloy composition according to claim 2, wherein said cast sheet has a mean centerline surface roughness Ra on the casting mold side of about 0.8 μm or less.

1. Field of the Invention

The present invention relates to a low boron amorphous alloy having excellent soft magnetic characteristics, and more specifically to a low boron amorphous alloy in which the boron content is advantageously reduced without deteriorating the magnetic characteristics of the alloy.

2. Description of the Related Art

Various Fe-Si-B alloy compositions are known to possess excellent soft magnetic characteristics.

For example, U.S. Pat. No. 3,856,513 discloses an amorphous alloy containing at least 80 at % Fe, at least 10 at % B and no more than 6 at % Si. Further, U.S. Pat. No. 235,064 discloses an amorphous alloy composed of 77-80 at % Fe, 12-16 at % B and 5-10 at % Si.

Almost all known Fe-Si-B amorphous alloys contain at least 10 at % B, as B is very important to the amorphous property of such alloys. The higher the B content, the stronger the amorphous forming capability of the alloys, whereby thermal stability is improved. Thus, it has been conventionally believed that a B content of at least 10 at % is required to produce excellent soft magnetic characteristics in Fe-Si-B amorphous alloys.

Further, both iron loss and magnetic flux density of conventional Fe-Si-B amorphous alloys containing less than 10 at % B are inferior to alloys containing at least 10 at % B.

Because of the high cost of B, there have been attempts to improve Fe-Si-B amorphous alloys containing less than 10 at % B. For example, C has been added to stabilize age deterioration and to improve amorphous property forming capabilities (Japanese Patent Unexamined Publication No. 57-145964 (1982) and Japanese Patent Unexamined Publication No. 58-42751 (1983)), Mn has been added to improve surface treatment properties (Japanese Patent Unexamined Publication No. 61-136660 (1986), and Cr has been added to improve casting properties (Japanese Patent Unexamined Publication No. 58-210154 (1983)). However, maintaining excellent soft magnetic characteristics in Fe-Si-B alloys containing less than 10 at % B has not been accomplished in the art.

An object of the present invention is to provide a low boron amorphous alloy having excellent soft magnetic characteristics.

Our investigations led to the discovery that the addition of a small amount of P (0.02-2 at %)accomplishes the above-described described object. More specifically, we discovered that this small addition of P greatly improves the surface roughness of a cast alloy, thereby maintaining excellent soft magnetic characteristics even at a B content below that of conventional amorphous alloys.

That is, the present invention relates to a low boron amorphous alloy having excellent soft magnetic characteristics and having the following composition:

B: about 6-10 at %;

Si: about 10-17 at %;

P: about 0.02-2 at %; and

the balance Fe and incidental impurities. Accordingly it is important that the balance shall consist essentially of Fe and incidental impurities, and that the alloy of this invention shall consist essentially of the above atomic percentage of B, Si and P.

Further, the present invention relates to a low boron amorphous alloy having excellent soft magnetic characteristics and having the following composition:

B: about 6-10 at %;

Si: about 10-17 at %;

P: about 0.02-2 at %;

C: about 0.1-2 at %; and

the balance Fe and incidental impurities. Accordingly it is important that the balance shall consist essentially of Fe and incidental impurities, and that the alloy of this invention shall consist essentially of the above atomic percentage of B, Si, P and C.

When low boron amorphous alloys according to the invention are cast into sheets by a single roll method or other conventional technique, the surface roughness of the cast sheet is reduced to where the mean centerline surface roughness Ra on the casting mold side is 0.8 μm or less.

FIG. 1 is a graph showing the relationship between B and P contents and surface roughness in a Fe-Si-B amorphous alloy; and

FIG. 2 is a graph showing the relationship between P content and iron loss in Fe-Si-B amorphous alloys having three different B contents.

FIG. 1 shows the results of an investigation into the effect of alloy composition on casting mold side surface roughness of cast alloys. This investigation was conducted on alloys comprising 78 at % Fe, and various quantities of Si, P and B. The alloys were made amorphous by conventional immediate-cooling techniques, such as the single roll method.

As seen in FIG. 1, the addition of P provides improved surface roughness at reduced B contents.

That is, an excellent mean centerline roughness of Ra ≦0.8 μm is obtained when P content is about 0.02-2 at % and B content is about 6-10 at %.

When alloys having compositions as described above are made amorphous using a conventional immediate-cooling device such as a single roll or the like, the surface roughness of resulting cast alloys can be limited to about 0.8 μm in terms of mean centerline roughness Ra on the casting mold side, whereby magnetic characteristics are improved.

It is preferable that the surface roughness Ra be about 0.6 μm or less to obtain even better magnetic characteristics.

FIG. 2 shows the results of an investigation into the relationship between P content and iron loss with respect to alloy sheets having the following compositions: Fe78 Si9-a B13 Pa (comparative example having a large B content), Fe78 Si14-a B8 Pa (example of the invention) and Fe78 Si16.5-a B5.5 Pa (comparative example having a small B content). As shown in FIG. 2, when B content is about 8 at %, excellent iron loss characteristics are obtained over a P content range of about 0.02-2 at %.

Although the thickness of the alloy sheet is not particularly limited, if cast too thin, surface roughness deteriorates and magnetic flux density decreases. If cast too thick, the rate of cooling is insufficient and iron loss deteriorates. Thus, it is preferable that the sheet thickness be about 17-25 μm so that such problems are eliminated.

A description will be given below of suitable contents for the elements comprising the amorphous alloy of the invention.

B: about 6-10 at %

The upper limit of B content in the invention is about 10 at %. If the B content exceeds about 10 at %, the surface roughness of the alloy sheet increases whereby soft magnetic characteristics deteriorate. Further, production costs soar due to the large quantity of expensive ferroboron used.

The lower B content limit is about 6 at %, as making an amorphous alloy becomes difficult when the B content is below about 6 at %.

A B content of about 7.5-9.5 at % is preferred when the cooling capacity limits of industrial production machines and material costs are taken into account.

Si: about 10-17 at %

Si contributes to reduced magnetostriction and to improved thermal stability of the cast alloy. When Si content is less than about 10 at %, the reduction of magnetostriction is insufficient, whereas when Si content exceeds about 17 at %, sheet brittleness becomes a problem. Thus, Si content is limited to about 10-17 at %.

P: about 0.02-2 at %

In this invention, P is a particularly important element as it is indispensable to the realization of excellent surface roughness and soft magnetic characteristics. When P content is below about 0.02 at %, surface roughness fails to improve sufficiently, whereas when P content exceeds about 2 at %, sheet brittleness increases and thermal stability declines. Thus, P content is limited to a range of about 0.02-2 at %.

In a wide sheet which requires strict brittleness control and excellent thermal stability, it is preferable that P content be about 0.02-0.5 at %.

C: about 0.1-2 at %

C improves soft magnetic characteristics and stabilizes the yield of B when P is added. However, when C content is less than about 0.1 at %, these beneficial effects are not sufficiently realized, whereas when C content exceeds about 2 at %, thermal stability of the sheet is reduced. Thus, C is contained in a range of about 0.1-2 at %.

To maintain product stability in commercial production, it is preferable that C content be within a range of about 0.1-1 at %.

The invention will now be described through illustrative examples. The examples are not intended to limit the scope of the invention defined in the solicited claims.

Various molten alloys having the compositions shown in Table 1 were cast onto the surface a cooling roll (roll diameter: 280 mm) rotating at a peripheral speed of 27 m/sec, thereby producing amorphous alloy sheets.

The following characteristics were evaluated on each amorphous alloy sheet: roughness on the casting mold side, iron loss, magnetic flux density and sheet thickness. The results of the evaluations are shown in Table 1.

As revealed in Table 1, when B content was 10 at % or less (below conventional B content) and P was added in accordance with the present invention, excellent soft magnetic characteristics (comparing favorably to those of conventional alloys having large B contents) were obtained.

According to the present invention, a low boron amorphous alloy having soft magnetic characteristics of the same quality as high boron amorphous alloys can be obtained. Consequently, the invention requires less B, thereby sharply reducing production costs.

Although this invention has been described in connection with specific forms thereof, it will be appreciated that equivalents may be substituted for the specific elements described herein without departing from the spirit and scope of the invention as defined in the appended claims.

TABLE 1
__________________________________________________________________________
(1)
Iron Magnetic
Surface
Loss Flux Thickness
Specimen
Composition Roughness
W13/50
Density
of Sheet
No. (at %) Ra (μm)
(W/kg)
B8 (T)
(μm)
Reference
__________________________________________________________________________
1 Fe78 Si9 B13
1.0 0.100
1.530
25 Conventional Example
2 Fe78 Si13.9 B8 P0.1
0.25 0.101
1.521
23 Example of the Invention
h3 Fe78 Si12.9 B9 P0.1
0.36 0.095
1.532
24 Example of the Invention
4 Fe78 Si13.4 B8.5 P0.1
0.32 0.103
1.524
22 Example of the Invention
5 Fe78 Si14.4 B9.5 P0.1
0.36 0.095
1.509
23 Example of the Invention
6 Fe78 Si11.9 B9 P0.1 C1
0.38 0.095
1.532
24 Example of the Invention
7 Fe78 Si9.9 B9 P0.1 C1
0.28 0.105
1.540
23 Example of the Invention
8 Fe78 Si16.4 B5.5 P0.1
1.50 2.305
0.985
24 Comparative Example
9 Fe78 Si10.9 B12 P0.1
0.95 0.121
1.505
25 Comparative Example
10 Fe78 Si8.9 B13 P0.1
0.92 0.132
1.506
26 Comparative Example
11 Fe78 Si13.5 B8.5
1.05 0.195
1.479
23 Comparative Example
12 Fe78 Si12.5 B9.5
0.93 0.184
1.482
25 Comparative Example
13 Fe78 Si13.98 B8 P0.02
0.61 0.101
1.500
18 Example of the Invention
14 Fe78 Si13.8 B8 P0.2
0.65 0.102
1.505
19 Example of the Invention
15 Fe78 Si12 B8 P2
0.79 0.106
1.500
20 Example of the Invention
__________________________________________________________________________
TABLE 1
__________________________________________________________________________
(2)
Iron Magnetic
Surface
Loss Flux Thickness
Specimen
Composition Roughness
W13/50
Density
of Sheet
No. (at %) Ra (μm)
(W/kg)
B8 (T)
(μm)
Reference
__________________________________________________________________________
16 Fe78 Si12.98 B8 P0.02 C1
0.41 0.102
1.504
20 Example of the Invention
17 Fe78 Si12.9 B8 P0.1 C1
0.53 0.101
1.505
19 Example of the Invention
18 Fe78 Si12.8 B8 P0.2 C1
0.54 0.103
1.506
17 Example of the Invention
19 Fe78 Si11 B8 P2 Cl1
0.69 0.105
1.510
19 Example of the Invention
20 Fe78 Si12.98 B9 P0.02
0.55 0.102
1.512
19 Example of the Invention
21 Fe78 Si12.8 B9 P0.2
0.58 0.098
1.514
18 Example of the Invention
22 Fe78 Si11 B9 P2
0.52 0.096
1.515
18 Example of the Invention
23 Fe78 Si11.98 B9 P0.02 C1
0.42 0.097
1.520
20 Example of the Invention
24 Fe78 Si11.8 B9 P0.2 C1
0.51 0.101
1.518
20 Example of the Invention
25 Fe78 Si11 B9 P2 C1
0.58 0.095
1.515
20 Example of the Invention
26 Fe78 Si11.98 B10 P0.02
0.50 0.094
1.520
19 Example of the Invention
27 Fe78 Si11.8 B10 P0.2
0.51 0.097
1.521
18 Example of the Invention
28 Fe78 Si10 B10 P2
0.53 0.098
1.523
23 Example of the Invention
29 Fe78 Si10.98 B10 P0.02 C1
0.43 0.095
1.524
19 Example of the Invention
30 Fe78 Si10.8 B10 P0.2 C1
0.42 0.094
1.520
19 Example of the Invention
__________________________________________________________________________
TABLE 1
__________________________________________________________________________
(3)
Iron Magnetic
Surface
Loss Flux Thickness
Specimen
Composition Roughness
W13/50
Density
of Sheet
No. (at %) Ra (μm)
(W/kg)
B8 (T)
(μm)
Reference
__________________________________________________________________________
31 Fe78 Si9 B10 P2 C1
0.54 0.098
1.518
20 Example of the Invention
32 Fe76 Si14.98 B9 P0.02
0.65 0.110
1.509
19 Example of the Invention
33 Fe76 Si14.8 B9 P0.2
0.64 0.108
1.508
18 Example of the Invention
34 Fe76 Si13 B9 P2
0.62 0.109
1.511
20 Example of the Invention
35 Fe76 Si13.98 B9 P0.02 C1
0.51 0.109
1.512
19 Example of the Invention
36 Fe76 Si13.8 B9 P0.2 C1
0.62 0.111
1.509
20 Example of the Invention
37 Fe76 Si12 B9 P2 C1
0.66 0.105
1.508
21 Example of the Invention
38 Fe76 Si14.48 B9.5 P0.02
0.43 0.080
1.503
18 Example of the Invention
39 Fe76 Si14.3 B9.5 P0.2
0.44 0.078
1.501
18 Example of the Invention
40 Fe76 Si12.5 B9.5 P2
0.57 0.083
1.505
18 Example of the Invention
41 Fe76 Si13.48 B9.5 P0.02 C1
0.49 0.095
1.503
19 Example of the Invention
42 Fe76 Si13.3 B9.5 P0.2 C1
0.58 0.093
1.504
21 Example of the Invention
43 Fe76 Si11.5 B9.5 P2 C1
0.53 0.097
1.505
19 Example of the Invention
44 Fe76 Si13.98 B10 P0.02
0.57 0.105
1.504
19 Example of the Invention
45 Fe76 Si13.8 B10 P0.2
0.53 0.102
1.505
21 Example of the Invention
__________________________________________________________________________
TABLE 1
__________________________________________________________________________
(4)
Iron Magnetic
Surface
Loss Flux Thickness
Specimen
Composition Roughness
W13/50
Density
of Sheet
No. (at %) Ra (μm)
(W/kg)
B8 (T)
(μm)
Reference
__________________________________________________________________________
46 Fe76 Si12 B10 P2
0.64 0.099
1.501
20 Example of the Invention
47 Fe76 Si12.98 B10 P0.02 C1
0.48 0.098
1.503
19 Example of the Invention
48 Fe76 Si12.8 B10 P0.2 C1
0.42 0.095
1.503
18 Example of the Invention
49 Fe76 Si11 B10 P2 Cl1
0.51 0.093
1.500
18 Example of the Invention
50 Fe80 Si11.98 B8 P0.02
0.64 0.096
1.345
18 Example of the Invention
51 Fe80 Si11.8 B8 P0.2
0.62 0.095
1.541
20 Example of the Invention
52 Fe80 Si10 B8 P2
0.59 0.102
1.525
20 Example of the Invention
53 Fe80 Si11.88 B8 P0.02 C0.1
0.55 0.098
1.542
23 Example of the Invention
54 Fe80 Si11.7 B8 P0.2 C0.1
0.61 0.100
1.540
21 Example of the Invention
55 Fe80 Si9.9 B1 P2 C0.1
0.55 0.102
1.523
20 Example of the Invention
56 Fe80 Si9.98 B8 P0.02 C2
0.49 0.096
1.541
19 Example of the Invention
57 Fe80 Si9.8 B8 P0.2 C2
0.50 0.098
1.538
19 Example of the Invention
58 Fe80 Si8 B8 P2 C2
0.51 0.104
1.526
18 Example of the Invention
59 Fe80 Si10.98 B9 P0.02
0.63 0.092
1.542
21 Example of the Invention
60 Fe80 Si10.8 B9 P0.2
0.61 0.094
1.543
19 Example of the Invention
__________________________________________________________________________
TABLE 1
__________________________________________________________________________
(5)
Iron Magnetic
Surface
Loss Flux Thickness
Specimen
Composition Roughness
W13/50
Density
of Sheet
No. (at %) Ra (μm)
(W/kg)
B8 (T)
(μm)
Reference
__________________________________________________________________________
61 Fe80 Si9 B9 P2
0.69 0.103
1.522
22 Example of the Invention
62 Fe80 Si10.88 B9 P0.02 C0.1
0.55 0.094
1.545
23 Example of the Invention
63 Fe80 Si10.7 B9 P0.2 C0.1
0.60 0.099
1.541
23 Example of the Invention
64 Fe80 Si8.9 B9 P2 C0.1
0.62 0.102
1.524
22 Example of the Invention
65 Fe80 Si8.98 B9 P0.02 C2
0.50 0.095
1.546
22 Example of the Invention
66 Fe80 Si8.8 B9 P0.2 C2
0.48 0.096
1.542
21 Example of the Invention
67 Fe80 Si7 B9 P2 C2
0.65 0.101
1.521
18 Example of the Invention
68 Fe80 Si9.98 B10 P0.02
0.64 0.088
1.541
19 Example of the Invention
69 Fe80 Si9.8 B10 P0.2
0.69 0.087
1.540
23 Example of the Invention
70 Fe80 Si8 B10 P2
0.72 0.099
1.523
19 Example of the Invention
71 Fe80 Si9.88 B10 P0.02 C0.1
0.68 0.089
1.545
18 Example of the Invention
72 Fe80 Si9.7 B10 P0.2 C0.1
0.61 0.087
1.546
22 Example of the Invention
73 Fe80 Si7.9 B10 P2 C0.1
0.57 0.100
1.522
20 Example of the Invention
74 Fe80 Si7.98 B10 P0.02 C2
0.49 0.094
1.545
21 Example of the Invention
75 Fe80 Si7.8 B10 P0.2 C2
0.48 0.095
1.547
21 Example of the Invention
__________________________________________________________________________
TABLE 1
__________________________________________________________________________
(6)
Iron Magnetic
Surface
Loss Flux Thickness
Specimen
Composition Roughness
W13/50
Density
of Sheet
No. (at %) Ra (μm)
(W/kg)
B8 (T)
(μm)
Reference
__________________________________________________________________________
76 Fe80 Si6 B10 P2 C2
0.55 0.102
1.526
22 Example of the Invention
77 Fe78 Si13.88 B8 P0.02 C0.1
0.59 0.094
1.535
19 Example of the Invention
78 Fe78 Si13.7 B8 P0.2 C0.1
0.68 0.098
1.532
23 Example of the Invention
79 Fe78 Si11.9 B8 P2 C0.1
0.72 0.100
1.515
18 Example of the Invention
80 Fe78 Si1.98 B8 P0.02 C2
0.75 0.092
1.534
19 Example of the Invention
81 Fe78 Si11.8 B8 P0.2 C2
0.71 0.091
1.532
20 Example of the Invention
82 Fe78 Si10 B8 P2 C2
0.69 0.102
1.516
18 Example of the Invention
83 Fe78 Si12.88 B9 P0.02 C0.1
0.51 0.096
1.536
18 Example of the Invention
84 Fe78 Si12.7 B9 P0.2 C0.1
0.57 0 .094
1.532
22 Example of the Invention
85 Fe78 Si10.9 B9 P2 C0.1
0.59 0.101
1.518
23 Example of the Invention
86 Fe78 Si10.98 B9 P0.02 C2
0.57 0.095
1.538
18 Example of the Invention
87 Fe78 Si10.8 B9 P0.2 C2
0.58 0.093
1.532
19 Example of the Invention
88 Fe78 Si9 B9 P2 C2
0.58 0.103
1.513
23 Example of the Invention
89 Fe78 Si11.88 B10 P0.02 C0.1
0.65 0 .093
1.536
21 Example of the Invention
90 Fe78 Si11.7 B10 P0.2 C0.1
0.67 0.094
1.531
20 Example of the Invention
__________________________________________________________________________
TABLE 1
__________________________________________________________________________
(7)
Iron Magnetic
Surface
Loss Flux Thickness
Specimen
Composition Roughness
W13/50
Density
of Sheet
No. (at %) Ra (μm)
(W/kg)
B8 (T)
(μm)
Reference
__________________________________________________________________________
91 Fe78 Si9.9 B10 P2 C0.1
0.70 0.100
1.514
21 Example of the Invention
92 Fe78 Si9.98 B10 P0.02 C2
0.52 0.092
1.538
23 Example of the Invention
93 Fe78 Si9.8 B10 P0.2 C2
0.54 0.093
1.534
22 Example of the Invention
94 Fe78 Si8 B10 P2 C2
0.55 0.101
1.513
23 Example of the Invention
95 Fe76 Si14.38 B9.5 P0.02 C0.1
0.64 0.078
1.520
20 Example of the Invention
96 Fe76 Si14.2 B9.5 P0.2 C0.1
0.63 0.082
1.515
18 Example of the Invention
97 Fe76 Si12.4 B9.5 P2 C0.1
0.70 0.088
1.490
18 Example of the Invention
98 Fe76 Si12.48 B9.5 P0.02 C2
0.55 0.075
1.521
19 Example of the Invention
99 Fe76 Si12.3 B9.5 P0.2 C2
0.54 0.076
1.518
22 Example of the Invention
100 Fe76 Si10.5 B9.5 P2 C2
0.59 0.079
1.491
21 Example of the Invention
__________________________________________________________________________

Kogiku, Fumio, Yukumoto, Masao, Matsuki, Kensuke

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Executed onAssignorAssigneeConveyanceFrameReelDoc
Aug 22 1995MATSUKI, KENSUKEKAWASAKI STEEL CORPORATION, A CORPORATION OF JAPANASSIGNMENT OF ASSIGNORS INTEREST SEE DOCUMENT FOR DETAILS 0076360197 pdf
Aug 22 1995YUKUMOTO, MASAOKAWASAKI STEEL CORPORATION, A CORPORATION OF JAPANASSIGNMENT OF ASSIGNORS INTEREST SEE DOCUMENT FOR DETAILS 0076360197 pdf
Aug 22 1995KOGIKU, FUMIOKAWASAKI STEEL CORPORATION, A CORPORATION OF JAPANASSIGNMENT OF ASSIGNORS INTEREST SEE DOCUMENT FOR DETAILS 0076360197 pdf
Aug 28 1995Kawasaki Steel Corporation(assignment on the face of the patent)
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